CN107284068A - Water-base ink indoors and outdoor inkjet printing design for advertisement method - Google Patents
Water-base ink indoors and outdoor inkjet printing design for advertisement method Download PDFInfo
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- CN107284068A CN107284068A CN201710521384.5A CN201710521384A CN107284068A CN 107284068 A CN107284068 A CN 107284068A CN 201710521384 A CN201710521384 A CN 201710521384A CN 107284068 A CN107284068 A CN 107284068A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0023—Digital printing methods characterised by the inks used
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0041—Digital printing on surfaces other than ordinary paper
- B41M5/0047—Digital printing on surfaces other than ordinary paper by ink-jet printing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses a kind of water-base ink indoors and outdoor inkjet printing design for advertisement method, comprise the following steps：(1) base material is provided, the base material is advertising cloth and/or poster paper；(2) water paint is coated at least one surface of the base material；(3) by water-base ink inkjet printing on the water-borne coating of the base material obtained by step (2), to obtain design for advertisement.Method this method of the present invention is not simply, conveniently, affected by environment, without using the solvent-based inks of high pollution, the features such as environmental protection, and the ink pattern have good weather resistance, strong water resistance and high abrasion, excellent combination property.
Description
Technical field
The invention belongs to inkjet technology field, more particularly it relates to which a kind of water-base ink is indoors and family
The method of outer inkjet printing design for advertisement.
Background technology
With the development of interior decoration industry and advertising sector, ink-jet technology is widely used.For example indoors
And the market demand of outdoor inkjet printing design for advertisement is increasing, can extensively see, be beaten by ink-jet in daily life
It is imprinted on the product that substrate surface shows various exquisite patterns.
The ink used in ink-jet technology has two kinds of water-based ink and oil-based ink.The properties of product of oil-based ink are preferable, but due to
Using poisonous and hazardous organic solvent, environmental pollution is serious, and the feature of environmental protection is poor, largely effects on it and uses scope.Water-based ink is cheap, peace
Entirely, word or picture definition height, organic solvent-resistant pollution-free, formed, thus the major demands as future market.But
It is that the outstanding problem of water-based ink is that the word that is sprayed into or image waterfastness performance, weather resistance and wearability be not good, therefore
It is difficult to the ink-jet products for obtaining excellent combination property.
On the matrixes such as paper, generally there is polymer coating, the ink or dyestuff of ejection is fixed on matrix.In order to carry
The water-fast property of high dyestuff, USP 5250107 proposes to add the polymer salt containing ammonium, zirconium in the composition of ink, increase dyestuff with
Hydrogen bond between matrix；USP 6106598 proposes to add silica gel colloid in ink；USP 6224660 proposes to add in ink siliceous
Organic polymer；USP 6001899 proposes to add containing quaternary ammonium salt cationic polymer and anionic dye formation sat linkage etc..But
It is that the above method can not solve water-fast, the weather-proof and wear-resisting problem of water-based ink simultaneously.In addition, abroad, generally significantly
Face ink jet printer requirement is used under conditions of certain temperature (such as 15-30 DEG C), humidity (such as relative humidity 35-60%).But China
Geographical environment and condition differ greatly, and the particularly Shelter in South China Cities summer humidity such as Changsha, Wuhan, Guangzhou, Nanchang is up to 90%, temperature
Often more than 36 DEG C.In addition, the domestic spray painted paper of China and overlay film coating quality index are sometimes up to the purpose less than fixed dye, from
And make air brushing formed dye image after printing (3-30 days) progressively produce dyestuff vacillate, particularly both at home and abroad commonly use dyestuff
Such as weld C.I. acid yellow 23s, the C.I. directly image of Huang 132 and part orchil as produced by C.I. acid reds 53
Vacillate to be serious, cause yellow and red text or image sharpness to reduce.Simultaneously, current solvent inkjet ink also has solvent
The three major issues such as volatilization causes environment very severe, Air seriously polluted and base material PVC is non-degradable, it would be highly desirable to solve.
Hence it is highly desirable to be formulated and technique improvement there is provided a kind of water-base ink indoors and outdoor ink-jet
The method of print ad pattern, this method is simple, conveniently, (temperature and humidity) not affected by environment, and can prepare tool simultaneously
There is the design for advertisement of high durable, high waterproof and high-wear resistance.
The content of the invention
In order to solve the above problems, one aspect of the present invention provides a kind of water-base ink indoors and outdoor inkjet printing
The method of design for advertisement, comprises the following steps：
(1) base material is provided, the base material is advertising cloth and/or poster paper；
(2) water paint is coated at least one surface of the base material；
(3) by water-base ink inkjet printing on the water-borne coating of the base material obtained by step (2), to obtain advertisement figure
Sample.
In one embodiment, the water paint, in parts by weight, its preparing raw material include following components：
Preferably, the water paint, in parts by weight, its preparing raw material include following components：
In one embodiment, the water paint, in parts by weight, its preparing raw material is also included：3-8 parts of sulfonation
Polyetheramine-sulfonated polyethersulfone block copolymer；Preferably, the sulfonated polyether amine-sulfonated polyethersulfone block copolymer is 5 parts.
In one embodiment, the water-base ink, in parts by weight, its preparing raw material include following components：
Preferably, the water-base ink, in parts by weight, its preparing raw material include following components：
In one embodiment, the water-base ink, in parts by weight, its preparing raw material is also included：1-5 parts of poly- season
Ammonium salt-polybenzimidazoles block copolymer；Preferably, the polyquaternium-polybenzimidazoles block copolymer is 3 parts.
In one embodiment, the pigment is selected from the black (MICROLITH of micro- high-tensile strength：Black) C-WA, micro- high-tensile strength are black
(MICROLITH：Black) C-K, carbon black, the red (MICROLITH of micro- high-tensile strength：Red) B-WA, the red (MICROLITH of micro- high-tensile strength：Red)
4C-K, micro- high-tensile strength indigo plant (MICROLITH：Blue) 4G-WA, micro- high-tensile strength indigo plant (MICROLITH：Blue) A3R-K, micro- high-tensile strength are yellow
(MICROLITH：Yellow) BAW-WA and micro- high-tensile strength Huang (MICROLITH：Yellow) at least one of 3R-K.
In one embodiment, the pigment dispersing agent is sodium naphthalene sulfonate condensation product (Ionet D-2) and dispersant A M-
C weight ratio is 0.6-0.9: 1 mixture；Preferably, the weight of sodium naphthalene sulfonate condensation product (Ionet D-2) and dispersant A M-C
Measure ratio 0.7: 1.
In one embodiment, other described auxiliary agents are TW-20 and/or QPE-20.
In one embodiment, the NMF is selected from glycerine, ethylene glycol, propane diols, polyethylene glycol, diethylene glycol (DEG), three
At least one of glycol and sorbierite.
In one embodiment, the surfactant is fluoro-alkyl alkoxide compound (Fluorad Fc171)
Or fluoroalkyl (Fluorad Fc430).
The above-mentioned of the application and other features, aspect and advantage is more readily understood with reference to described further below.
Embodiment
The participation in the election detailed description of the invention below for being preferable to carry out method and including embodiment this public affairs can be more easily understood
Open content.A large amount of terms can be referred in description below and claims, these terms are defined as following meanings.
Singulative includes plural number and object is discussed, unless the context clearly dictates otherwise.
In some examples, approximate term likely corresponds to the precision of the instrument of measured value.In present specification and
In claims, scope limits and can combine and/or exchange, and these scopes include contained therebetween if not stated otherwise
All subranges.
One aspect of the present invention provide a kind of water-base ink indoors and outdoor inkjet printing design for advertisement method, bag
Include following steps：
(1) base material is provided, the base material is advertising cloth and/or poster paper；
(2) water paint is coated at least one surface of the base material；
(3) by water-base ink inkjet printing on the water-borne coating of the base material obtained by step (2), to obtain advertisement figure
Sample.
Water paint
Water paint for the application is not particularly limited, and can be commercialized product or be synthesized by experiment
Arrive.Such as described water paint, in parts by weight, its preparing raw material include following components：
Preferably, the water paint, in parts by weight, its preparing raw material include following components：
For further improving performance, the water paint, in parts by weight, its preparing raw material are also included：3-8 parts
Sulfonated polyether amine-sulfonated polyethersulfone block copolymer；Preferably, the sulfonated polyether amine-sulfonated polyethersulfone block copolymer is 5
Part.
In one embodiment, the method for the sulfonated polyether amine-sulfonated polyethersulfone block copolymer includes following step
Suddenly：
(1) preparation of polyetheramine prepolymer
In the three-necked bottle that 1000mL is dried, 100 grams of octafluorobiphenyl diglycidyl ether (epoxide number is sequentially added
0.45mol/100g), 0.22mol benzylamine and 700 grams of dimethyl sulfoxide (DMSO)s, lead to nitrogen protection and magnetic agitation；1h is stirred at room temperature
Afterwards, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room temperature, obtains epoxy-capped polyetheramine pre-polymer solution；
(2) preparation of polyetheramine-sulfonated polyethersulfone block copolymer
In the three-necked bottle that 1000mL is dried, weigh respectively 0.0105mol sulfonation dichloro diphenyl sulfone, 0.01mol grams
4,4'- '-biphenyl diphenols, are dissolved in 50mL 1-METHYLPYRROLIDONE (NMP), add 0.03mol sodium carbonate and 20mL first
Benzene, lead to nitrogen protect 1 hour after, by reaction system at 180 DEG C sustained response 24 hours, be then down to room temperature, add
After 0.0005mol para-aminophenol, lead to nitrogen protect 1 hour after, by reaction system at 180 DEG C sustained response 12 hours
Afterwards, room temperature is down to, dark brown viscous liquid is obtained, the epoxy-capped polyetheramine prepolymer for then obtaining above-mentioned steps (1) is molten
Liquid all adds this reaction system, after leading to nitrogen protection 1 hour, heats up 80 DEG C after reacting 4 hours, reaction solution is poured into rapidly
In 2000mL deionized waters, a large amount of solid precipitations are obtained；With after the deionized water cyclic washing product, suction filtration simultaneously collects polymerization
Thing, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain polyetheramine-sulfonated polyethersulfone block copolymer；
(3) preparation of sulfonated polyether amine-sulfonated polyethersulfone block copolymer
Polyetheramine-sulfonated polyethersulfone block copolymer 1 gram obtained by taking step (2), is dissolved in the dense sulphur of mass fraction 98%
In acid, after being reacted 5 hours under ice bath, pour into frozen water, with after the frozen water cyclic washing product, suction filtration and collected polymer, in
In vacuum drying oven, 50 DEG C of dryings 24 hours obtain sulfonated polyether amine-sulfonated polyethersulfone block copolymer.
In one embodiment, the preparation method of above-mentioned water paint is：
Described material component is added and is sufficiently mixed in mixer after 20 minutes, discharging is obtained.
Water-base ink
Water paint for the application is not particularly limited, and can be commercialized product or be synthesized by experiment
Arrive.Such as described water paint, in parts by weight, its preparing raw material include following components：
Its preparing raw material includes following components：
Preferably, the water-base ink, in parts by weight, its preparing raw material include following components：
It is highly preferred that the water-base ink, in parts by weight, its preparing raw material include following components：
For further improving performance, the water-base ink, in parts by weight, its preparing raw material are also included：1-5 parts
Polyquaternium-polybenzimidazoles block copolymer；Preferably, the polyquaternium-polybenzimidazoles block copolymer is 3 parts.
In one embodiment, the preparation method of the polyquaternium-polybenzimidazoles block copolymer includes following
Step：
(1) polyquaternium prepolymer is prepared
In the three-necked bottle that 1000ml is dried, 1,12- dibromo-dodecanes 0.1mol, Isosorbide-5-Nitrae-lupetazin are added
0.097mol and solvent dimethyl sulfoxide (DMSO) 80ml, at 50 DEG C after reaction 5 hours, vacuum distillation removes solvent and obtains polyquaternium
Prepolymer；
(2) polybenzimidazoles prepolymer is prepared
180g polyphosphoric acids is placed in 250ml three-neck flasks, connection nitrogen inlet, drying tube, nitrogen outlet and machinery
Agitator.After nitrogen is passed through 5 minutes, 0.01mol 3,3'- diaminobenzidines (DAB) are added in three-neck flask, treated
DAB is uniformly dispersed after being dissolved in polyphosphoric acids, adds 0.009mmol terephthalic acid (TPA)s, and 20mmol P is added afterwards2O5
For the water generated in absorbing reaction, open mechanical agitation and heat up simultaneously, keep 200 DEG C of reaction 20h.Question response system temperature is cold
But precipitate to after 150 DEG C, pouring into deionized water, cyclic washing removes polyphosphoric acids.With the hydrogen-oxygen of a large amount of mass fractions 10%
Change sodium water solution agitator treating and neutralize the phosphoric acid of residual in 24 hours, then sodium hydroxide is repeatedly removed with deionization cyclic washing.Will
Gained is deposited in vacuum drying oven at 60 DEG C and dried, and produces polybenzimidazoles prepolymer；
(3) polyquaternium-polybenzimidazoles block copolymer is prepared
In the three-necked bottle that 1000ml is dried, polyquaternium prepolymer, 1 gram of step obtained by 1 gram of step (1) are sequentially added
(2) gained polybenzimidazoles prepolymer, 100ml dimethyl sulfoxide (DMSO)s and 2 grams of sodium carbonate, after being reacted 5 hours at 60 DEG C, are obtained
Clear yellow viscous solution, is down to after room temperature, pours into deionized water and precipitates, and with deionization cyclic washing repeatedly to neutral, then takes out
Filter, collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain polyquaternium-polybenzimidazoles block copolymer.
It is preferably carried out in one kind in mode, above-mentioned water paint, in parts by weight, its preparing raw material are also included：5 parts
Sulfonated polyether ketone modified graphene oxide, and the preparation method of the sulfonated polyether ketone modified graphene oxide is：
In the three-necked bottle that 1000mL is dried, 0.0106mol sulfonation 4 is weighed respectively, 4'- difluoro benzophenones,
0.01mol grams of 4,4'- '-biphenyl diphenols, are dissolved in 50mL 1-METHYLPYRROLIDONE (NMP), add 0.03mol carbonic acid
The toluene of sodium and 20mL, lead to nitrogen protect 1 hour after, by reaction system at 180 DEG C sustained response 24 hours, be then down to room
Temperature, add 0.0006mol para-aminophenol after, lead to nitrogen protect 1 hour after, by reaction system at 180 DEG C sustained response
After 12 hours, be down to room temperature, obtain dark brown viscous liquid, then into this reaction system add 30 grams of graphene oxides and
5 grams of KH-560, lead to nitrogen protect 1 hour after, heat up 80 DEG C reaction 4 hours after, reaction solution is poured into rapidly 2000mL go from
In sub- water, a large amount of solid precipitations are obtained；With after the deionized water cyclic washing product, suction filtration and collected polymer dry in vacuum
In case, 50 DEG C of dryings 24 hours obtain sulfonated polyether ketone modified graphene oxide.
In one embodiment, the preparation method of above-mentioned water-base ink is：
Described material component is added and is sufficiently mixed in mixer after 30 minutes, discharging is obtained.
Pigment
Pigment for the application is not particularly limited, and can be commercialized product or be obtained by testing synthesis.
In one embodiment, the pigment is selected from the black (MICROLITH of micro- high-tensile strength：Black) C-WA, micro- high-tensile strength are black
(MICROLITH：Black) C-K, carbon black, the red (MICROLITH of micro- high-tensile strength：Red) B-WA, the red (MICROLITH of micro- high-tensile strength：Red)
4C-K, micro- high-tensile strength indigo plant (MICROLITH：Blue) 4G-WA, micro- high-tensile strength indigo plant (MICROLITH：Blue) A3R-K, micro- high-tensile strength are yellow
(MICROLITH：Yellow) BAW-WA and micro- high-tensile strength Huang (MICROLITH：Yellow) at least one of 3R-K.
Pigment dispersing agent
Pigment dispersing agent for the application is not particularly limited, and can be commercialized product or be synthesized by testing
Obtain.In one embodiment, the pigment dispersing agent is sodium naphthalene sulfonate condensation product (Ionet D-2) and dispersant A M-C's
Weight ratio is 0.6-0.9: 1 mixture；Preferably, the weight of sodium naphthalene sulfonate condensation product (Ionet D-2) and dispersant A M-C
Than 0.7: 1.
Other auxiliary agents
Other auxiliary agents for the application are not particularly limited, and can be commercialized product or be synthesized by experiment
Arrive.In one embodiment, the auxiliary agent is TW-20 and/or QPE-20.
NMF
NMF for the application is not particularly limited, and can be commercialized product or be synthesized by experiment
Arrive.In one embodiment, the NMF be selected from glycerine, ethylene glycol, propane diols, polyethylene glycol, diethylene glycol (DEG), triethylene glycol with
At least one of and sorbierite.
Surfactant
In one embodiment, the surfactant is fluoro-alkyl alkoxide compound (Fluorad Fc171)
Or fluoroalkyl (Fluorad Fc430).
The present invention is specifically described below by embodiment.It is necessarily pointed out that, following examples are only used
In the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field
Some the nonessential modifications and adaptations made according to the content of the invention described above, still fall within protection scope of the present invention.
In addition, if without other explanations, raw materials used is all commercially available, and number used in following material is weight
Part.
Embodiment 1
Water paint coating liquid is sprayed on to the surface of advertising cloth with the method for spraying, with roll shaft by advertising cloth face coat
Roll it is even roll reality, dried in baking oven, drying temperature be 80 degrees Celsius, drying time be 50 minutes；
With ink jet printer by water-base ink inkjet printing on the water-borne coating of the base material obtained by step (2), with obtain
Design for advertisement；
The preparation method of the water paint is：
By 5 grams of hydroxyethyl cellulose, 10 grams of acrylic emulsion, 0.1 gram of APES, 3 grams of second
Glycol, 1 gram of methyl-silicone oil, 5 grams of butyl and 100 grams of deionized water, which are added in mixer, is sufficiently mixed 20
After minute, discharging is obtained；
The preparation method of the water-base ink is：
By 1 gram of the black (MICROLITH of micro- high-tensile strength：Black) C-WA, 1 gram of pigment dispersing agent (sodium naphthalene sulfonate condensation product
(Ionet D-2) and dispersant A M-C weight ratio are 0.6: 1 mixture), 10 grams of glycerine, 1 gram of TW-20,0.001 gram
Fluoro-alkyl alkoxide compound (Fluorad Fc171) and 100 grams deionized water add mixer in be sufficiently mixed
After 30 minutes, discharging is obtained.
Embodiment 2
Water paint coating liquid is sprayed on to the surface of advertising cloth with the method for spraying, with roll shaft by advertising cloth face coat
Roll it is even roll reality, dried in baking oven, drying temperature be 80 degrees Celsius, drying time be 50 minutes；
With ink jet printer by water-base ink inkjet printing on the water-borne coating of the base material obtained by step (2), with obtain
Design for advertisement；
The preparation method of the water paint is：
By 10 grams of hydroxyethyl cellulose, 30 grams of acrylic emulsion, 2 grams of APES, 10 grams of second
Glycol, 5 grams of methyl-silicone oil, 10 grams of butyl and 100 grams of deionized water are added to be sufficiently mixed in mixer
After 20 minutes, discharging is obtained；
The preparation method of the water-base ink is：
By 10 grams of the black (MICROLITH of micro- high-tensile strength：Black) C-WA, 10 grams of pigment dispersing agent (sodium naphthalene sulfonate condensation product
(Ionet D-2) and dispersant A M-C weight ratio are 0.6: 1 mixture), 30 grams of glycerine, 5 grams of TW-20,0.05 gram
Fluoro-alkyl alkoxide compound (Fluorad Fc171) and 100 grams deionized water add mixer in be sufficiently mixed
After 30 minutes, discharging is obtained.
Embodiment 3
Water paint coating liquid is sprayed on to the surface of advertising cloth with the method for spraying, with roll shaft by advertising cloth face coat
Roll it is even roll reality, dried in baking oven, drying temperature be 80 degrees Celsius, drying time be 50 minutes；
With ink jet printer by water-base ink inkjet printing on the water-borne coating of the base material obtained by step (2), with obtain
Design for advertisement；
The preparation method of the water paint is：
By 6 grams of hydroxyethyl cellulose, 15 grams of acrylic emulsion, 0.5 gram of APES, 8 grams of second
Glycol, 3 grams of methyl-silicone oil, 7 grams of butyl and 100 grams of deionized water, which are added in mixer, is sufficiently mixed 20
After minute, discharging is obtained；
The preparation method of the water-base ink is：
By 3 grams of the black (MICROLITH of micro- high-tensile strength：Black) C-WA, 3 grams of pigment dispersing agent (sodium naphthalene sulfonate condensation product
(Ionet D-2) and dispersant A M-C weight ratio are 0.6: 1 mixture), 20 grams of glycerine, 3 grams of TW-20,0.02 gram
Fluoro-alkyl alkoxide compound (Fluorad Fc171) and 100 grams deionized water add mixer in be sufficiently mixed
After 30 minutes, discharging is obtained.
Embodiment 4
Water paint coating liquid is sprayed on to the surface of advertising cloth with the method for spraying, with roll shaft by advertising cloth face coat
Roll it is even roll reality, dried in baking oven, drying temperature be 80 degrees Celsius, drying time be 50 minutes；
With ink jet printer by water-base ink inkjet printing on the water-borne coating of the base material obtained by step (2), with obtain
Design for advertisement；
The preparation method of the water paint is：
By 6 grams of hydroxyethyl cellulose, 15 grams of acrylic emulsion, 0.5 gram of APES, 8 grams of second
Glycol, 3 grams of methyl-silicone oil, 7 grams of butyl and 100 grams of deionized water, which are added in mixer, is sufficiently mixed 20
After minute, discharging is obtained；
The preparation method of the water-base ink is：
By 3 grams of the black (MICROLITH of micro- high-tensile strength：Black) C-WA, 3 grams of pigment dispersing agent (sodium naphthalene sulfonate condensation product
(Ionet D-2) and dispersant A M-C weight ratio are 0.7: 1 mixture), 20 grams of glycerine, 3 grams of TW-20,0.02 gram
Fluoro-alkyl alkoxide compound (Fluorad Fc171) and 100 grams deionized water add mixer in be sufficiently mixed
After 30 minutes, discharging is obtained.
Embodiment 5
Water paint coating liquid is sprayed on to the surface of advertising cloth with the method for spraying, with roll shaft by advertising cloth face coat
Roll it is even roll reality, dried in baking oven, drying temperature be 80 degrees Celsius, drying time be 50 minutes；
With ink jet printer by water-base ink inkjet printing on the water-borne coating of the base material obtained by step (2), with obtain
Design for advertisement；
The preparation method of the water paint is：
By 6 grams of hydroxyethyl cellulose, 15 grams of acrylic emulsion, 0.5 gram of APES, 8 grams of second
Glycol, 3 grams of methyl-silicone oil, 7 grams of butyl, 3 grams of sulfonated polyether amine-sulfonated polyethersulfone block copolymer be with
And 100 grams deionized water add mixer in be sufficiently mixed after 20 minutes, discharging is obtained, wherein sulfonated polyether amine-sulphur
Change polyethersulfone block copolymer preparation method be：
(1) preparation of polyetheramine prepolymer
In the three-necked bottle that 1000mL is dried, 100 grams of octafluorobiphenyl diglycidyl ether (epoxide number is sequentially added
0.45mol/100g), 0.22mol benzylamine and 700 grams of dimethyl sulfoxide (DMSO)s, lead to nitrogen protection and magnetic agitation；1h is stirred at room temperature
Afterwards, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room temperature, obtains epoxy-capped polyetheramine pre-polymer solution；
(2) preparation of polyetheramine-sulfonated polyethersulfone block copolymer
In the three-necked bottle that 1000mL is dried, weigh respectively 0.0105mol sulfonation dichloro diphenyl sulfone, 0.01mol grams
4,4'- '-biphenyl diphenols, are dissolved in 50mL 1-METHYLPYRROLIDONE (NMP), add 0.03mol sodium carbonate and 20mL first
Benzene, lead to nitrogen protect 1 hour after, by reaction system at 180 DEG C sustained response 24 hours, be then down to room temperature, add
After 0.0005mol para-aminophenol, lead to nitrogen protect 1 hour after, by reaction system at 180 DEG C sustained response 12 hours
Afterwards, room temperature is down to, dark brown viscous liquid is obtained, the epoxy-capped polyetheramine prepolymer for then obtaining above-mentioned steps (1) is molten
Liquid all adds this reaction system, after leading to nitrogen protection 1 hour, heats up 80 DEG C after reacting 4 hours, reaction solution is poured into rapidly
In 2000mL deionized waters, a large amount of solid precipitations are obtained；With after the deionized water cyclic washing product, suction filtration simultaneously collects polymerization
Thing, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain polyetheramine-sulfonated polyethersulfone block copolymer；
(3) preparation of sulfonated polyether amine-sulfonated polyethersulfone block copolymer
Polyetheramine-sulfonated polyethersulfone block copolymer 1 gram obtained by taking step (2), is dissolved in the dense sulphur of mass fraction 98%
In acid, after being reacted 5 hours under ice bath, pour into frozen water, with after the frozen water cyclic washing product, suction filtration and collected polymer, in
In vacuum drying oven, 50 DEG C of dryings 24 hours obtain sulfonated polyether amine-sulfonated polyethersulfone block copolymer；
The preparation method of the water-base ink is：
By 3 grams of the black (MICROLITH of micro- high-tensile strength：Black) C-WA, 3 grams of pigment dispersing agent (sodium naphthalene sulfonate condensation product
(Ionet D-2) and dispersant A M-C weight ratio are 0.7: 1 mixture), 20 grams of glycerine, 3 grams of TW-20,0.02 gram
Fluoro-alkyl alkoxide compound (Fluorad Fc171) and 100 grams deionized water add mixer in be sufficiently mixed
After 30 minutes, discharging is obtained.
Embodiment 6
Water paint coating liquid is sprayed on to the surface of advertising cloth with the method for spraying, with roll shaft by advertising cloth face coat
Roll it is even roll reality, dried in baking oven, drying temperature be 80 degrees Celsius, drying time be 50 minutes；
With ink jet printer by water-base ink inkjet printing on the water-borne coating of the base material obtained by step (2), with obtain
Design for advertisement；
The preparation method of the water paint is：
By 6 grams of hydroxyethyl cellulose, 15 grams of acrylic emulsion, 0.5 gram of APES, 8 grams of second
Glycol, 3 grams of methyl-silicone oil, 7 grams of butyl, 8 grams of sulfonated polyether amine-sulfonated polyethersulfone block copolymer be with
And 100 grams deionized water add mixer in be sufficiently mixed after 20 minutes, discharging is obtained, wherein sulfonated polyether amine-sulphur
Change polyethersulfone block copolymer preparation method be：
(1) preparation of polyetheramine prepolymer
In the three-necked bottle that 1000mL is dried, 100 grams of octafluorobiphenyl diglycidyl ether (epoxide number is sequentially added
0.45mol/100g), 0.22mol benzylamine and 700 grams of dimethyl sulfoxide (DMSO)s, lead to nitrogen protection and magnetic agitation；1h is stirred at room temperature
Afterwards, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room temperature, obtains epoxy-capped polyetheramine pre-polymer solution；
(2) preparation of polyetheramine-sulfonated polyethersulfone block copolymer
In the three-necked bottle that 1000mL is dried, weigh respectively 0.0105mol sulfonation dichloro diphenyl sulfone, 0.01mol grams
4,4'- '-biphenyl diphenols, are dissolved in 50mL 1-METHYLPYRROLIDONE (NMP), add 0.03mol sodium carbonate and 20mL first
Benzene, lead to nitrogen protect 1 hour after, by reaction system at 180 DEG C sustained response 24 hours, be then down to room temperature, add
After 0.0005mol para-aminophenol, lead to nitrogen protect 1 hour after, by reaction system at 180 DEG C sustained response 12 hours
Afterwards, room temperature is down to, dark brown viscous liquid is obtained, the epoxy-capped polyetheramine prepolymer for then obtaining above-mentioned steps (1) is molten
Liquid all adds this reaction system, after leading to nitrogen protection 1 hour, heats up 80 DEG C after reacting 4 hours, reaction solution is poured into rapidly
In 2000mL deionized waters, a large amount of solid precipitations are obtained；With after the deionized water cyclic washing product, suction filtration simultaneously collects polymerization
Thing, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain polyetheramine-sulfonated polyethersulfone block copolymer；
(3) preparation of sulfonated polyether amine-sulfonated polyethersulfone block copolymer
Polyetheramine-sulfonated polyethersulfone block copolymer 1 gram obtained by taking step (2), is dissolved in the dense sulphur of mass fraction 98%
In acid, after being reacted 5 hours under ice bath, pour into frozen water, with after the frozen water cyclic washing product, suction filtration and collected polymer, in
In vacuum drying oven, 50 DEG C of dryings 24 hours obtain sulfonated polyether amine-sulfonated polyethersulfone block copolymer；
The preparation method of the water-base ink is：
By 3 grams of the black (MICROLITH of micro- high-tensile strength：Black) C-WA, 3 grams of pigment dispersing agent (sodium naphthalene sulfonate condensation product
(Ionet D-2) and dispersant A M-C weight ratio are 0.7: 1 mixture), 20 grams of glycerine, 3 grams of TW-20,0.02 gram
Fluoro-alkyl alkoxide compound (Fluorad Fc171) and 100 grams deionized water add mixer in be sufficiently mixed
After 30 minutes, discharging is obtained.
Embodiment 7
Water paint coating liquid is sprayed on to the surface of advertising cloth with the method for spraying, with roll shaft by advertising cloth face coat
Roll it is even roll reality, dried in baking oven, drying temperature be 80 degrees Celsius, drying time be 50 minutes；
With ink jet printer by water-base ink inkjet printing on the water-borne coating of the base material obtained by step (2), with obtain
Design for advertisement；
The preparation method of the water paint is：
By 6 grams of hydroxyethyl cellulose, 15 grams of acrylic emulsion, 0.5 gram of APES, 8 grams of second
Glycol, 3 grams of methyl-silicone oil, 7 grams of butyl, 5 grams of sulfonated polyether amine-sulfonated polyethersulfone block copolymer be with
And 100 grams deionized water add mixer in be sufficiently mixed after 20 minutes, discharging is obtained, wherein sulfonated polyether amine-sulphur
Change polyethersulfone block copolymer preparation method be：
(1) preparation of polyetheramine prepolymer
In the three-necked bottle that 1000mL is dried, 100 grams of octafluorobiphenyl diglycidyl ether (epoxide number is sequentially added
0.45mol/100g), 0.22mol benzylamine and 700 grams of dimethyl sulfoxide (DMSO)s, lead to nitrogen protection and magnetic agitation；1h is stirred at room temperature
Afterwards, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room temperature, obtains epoxy-capped polyetheramine pre-polymer solution；
(2) preparation of polyetheramine-sulfonated polyethersulfone block copolymer
In the three-necked bottle that 1000mL is dried, weigh respectively 0.0105mol sulfonation dichloro diphenyl sulfone, 0.01mol grams
4,4'- '-biphenyl diphenols, are dissolved in 50mL 1-METHYLPYRROLIDONE (NMP), add 0.03mol sodium carbonate and 20mL first
Benzene, lead to nitrogen protect 1 hour after, by reaction system at 180 DEG C sustained response 24 hours, be then down to room temperature, add
After 0.0005mol para-aminophenol, lead to nitrogen protect 1 hour after, by reaction system at 180 DEG C sustained response 12 hours
Afterwards, room temperature is down to, dark brown viscous liquid is obtained, the epoxy-capped polyetheramine prepolymer for then obtaining above-mentioned steps (1) is molten
Liquid all adds this reaction system, after leading to nitrogen protection 1 hour, heats up 80 DEG C after reacting 4 hours, reaction solution is poured into rapidly
In 2000mL deionized waters, a large amount of solid precipitations are obtained；With after the deionized water cyclic washing product, suction filtration simultaneously collects polymerization
Thing, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain polyetheramine-sulfonated polyethersulfone block copolymer；
(3) preparation of sulfonated polyether amine-sulfonated polyethersulfone block copolymer
Polyetheramine-sulfonated polyethersulfone block copolymer 1 gram obtained by taking step (2), is dissolved in the dense sulphur of mass fraction 98%
In acid, after being reacted 5 hours under ice bath, pour into frozen water, with after the frozen water cyclic washing product, suction filtration and collected polymer, in
In vacuum drying oven, 50 DEG C of dryings 24 hours obtain sulfonated polyether amine-sulfonated polyethersulfone block copolymer；
The preparation method of the water-base ink is：
By 3 grams of the black (MICROLITH of micro- high-tensile strength：Black) C-WA, 3 grams of pigment dispersing agent (sodium naphthalene sulfonate condensation product
(Ionet D-2) and dispersant A M-C weight ratio are 0.7: 1 mixture), 20 grams of glycerine, 3 grams of TW-20,0.02 gram
Fluoro-alkyl alkoxide compound (Fluorad Fc171) and 100 grams deionized water add mixer in be sufficiently mixed
After 30 minutes, discharging is obtained.
Embodiment 8
Water paint coating liquid is sprayed on to the surface of advertising cloth with the method for spraying, with roll shaft by advertising cloth face coat
Roll it is even roll reality, dried in baking oven, drying temperature be 80 degrees Celsius, drying time be 50 minutes；
With ink jet printer by water-base ink inkjet printing on the water-borne coating of the base material obtained by step (2), with obtain
Design for advertisement；
The preparation method of the water paint is：
By 6 grams of hydroxyethyl cellulose, 15 grams of acrylic emulsion, 0.5 gram of APES, 8 grams of second
Glycol, 3 grams of methyl-silicone oil, 7 grams of butyl, 5 grams of sulfonated polyether amine-sulfonated polyethersulfone block copolymer be with
And 100 grams deionized water add mixer in be sufficiently mixed after 20 minutes, discharging is obtained, wherein sulfonated polyether amine-sulphur
Change polyethersulfone block copolymer preparation method be：
(1) preparation of polyetheramine prepolymer
In the three-necked bottle that 1000mL is dried, 100 grams of octafluorobiphenyl diglycidyl ether (epoxide number is sequentially added
0.45mol/100g), 0.22mol benzylamine and 700 grams of dimethyl sulfoxide (DMSO)s, lead to nitrogen protection and magnetic agitation；1h is stirred at room temperature
Afterwards, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room temperature, obtains epoxy-capped polyetheramine pre-polymer solution；
(2) preparation of polyetheramine-sulfonated polyethersulfone block copolymer
In the three-necked bottle that 1000mL is dried, weigh respectively 0.0105mol sulfonation dichloro diphenyl sulfone, 0.01mol grams
4,4'- '-biphenyl diphenols, are dissolved in 50mL 1-METHYLPYRROLIDONE (NMP), add 0.03mol sodium carbonate and 20mL first
Benzene, lead to nitrogen protect 1 hour after, by reaction system at 180 DEG C sustained response 24 hours, be then down to room temperature, add
After 0.0005mol para-aminophenol, lead to nitrogen protect 1 hour after, by reaction system at 180 DEG C sustained response 12 hours
Afterwards, room temperature is down to, dark brown viscous liquid is obtained, the epoxy-capped polyetheramine prepolymer for then obtaining above-mentioned steps (1) is molten
Liquid all adds this reaction system, after leading to nitrogen protection 1 hour, heats up 80 DEG C after reacting 4 hours, reaction solution is poured into rapidly
In 2000mL deionized waters, a large amount of solid precipitations are obtained；With after the deionized water cyclic washing product, suction filtration simultaneously collects polymerization
Thing, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain polyetheramine-sulfonated polyethersulfone block copolymer；
(3) preparation of sulfonated polyether amine-sulfonated polyethersulfone block copolymer
Polyetheramine-sulfonated polyethersulfone block copolymer 1 gram obtained by taking step (2), is dissolved in the dense sulphur of mass fraction 98%
In acid, after being reacted 5 hours under ice bath, pour into frozen water, with after the frozen water cyclic washing product, suction filtration and collected polymer, in
In vacuum drying oven, 50 DEG C of dryings 24 hours obtain sulfonated polyether amine-sulfonated polyethersulfone block copolymer；
The preparation method of the water-base ink is：
By 3 grams of the black (MICROLITH of micro- high-tensile strength：Black) C-WA, 3 grams of pigment dispersing agent (sodium naphthalene sulfonate condensation product
(Ionet D-2) and dispersant A M-C weight ratio are 0.7: 1 mixture), 20 grams of glycerine, 3 grams of TW-20,0.02 gram
Fluoro-alkyl alkoxide compound (Fluorad Fc171), 1 gram of polyquaternium-polybenzimidazoles block copolymer and
100 grams of deionized water is added to be sufficiently mixed after 30 minutes in mixer, and discharging is obtained；
The preparation method of the polyquaternium-polybenzimidazoles block copolymer is：
(1) polyquaternium prepolymer is prepared
In the three-necked bottle that 1000ml is dried, 1,12- dibromo-dodecanes 0.1mol, Isosorbide-5-Nitrae-lupetazin are added
0.097mol and solvent dimethyl sulfoxide (DMSO) 80ml, at 50 DEG C after reaction 5 hours, vacuum distillation removes solvent and obtains polyquaternium
Prepolymer；
(2) polybenzimidazoles prepolymer is prepared
180g polyphosphoric acids is placed in 250ml three-neck flasks, connection nitrogen inlet, drying tube, nitrogen outlet and machinery
Agitator.After nitrogen is passed through 5 minutes, 0.01mol 3,3'- diaminobenzidines (DAB) are added in three-neck flask, treated
DAB is uniformly dispersed after being dissolved in polyphosphoric acids, adds 0.009mmol terephthalic acid (TPA)s, and 20mmol P is added afterwards2O5
For the water generated in absorbing reaction, open mechanical agitation and heat up simultaneously, keep 200 DEG C of reaction 20h.Question response system temperature is cold
But precipitate to after 150 DEG C, pouring into deionized water, cyclic washing removes polyphosphoric acids.With the hydrogen-oxygen of a large amount of mass fractions 10%
Change sodium water solution agitator treating and neutralize the phosphoric acid of residual in 24 hours, then sodium hydroxide is repeatedly removed with deionization cyclic washing.Will
Gained is deposited in vacuum drying oven at 60 DEG C and dried, and produces polybenzimidazoles prepolymer；
(3) polyquaternium-polybenzimidazoles block copolymer is prepared
In the three-necked bottle that 1000ml is dried, polyquaternium prepolymer, 1 gram of step obtained by 1 gram of step (1) are sequentially added
(2) gained polybenzimidazoles prepolymer, 100ml dimethyl sulfoxide (DMSO)s and 2 grams of sodium carbonate, after being reacted 5 hours at 60 DEG C, are obtained
Clear yellow viscous solution, is down to after room temperature, pours into deionized water and precipitates, and with deionization cyclic washing repeatedly to neutral, then takes out
Filter, collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain polyquaternium-polybenzimidazoles block copolymer.
Embodiment 9
Water paint coating liquid is sprayed on to the surface of advertising cloth with the method for spraying, with roll shaft by advertising cloth face coat
Roll it is even roll reality, dried in baking oven, drying temperature be 80 degrees Celsius, drying time be 50 minutes；
With ink jet printer by water-base ink inkjet printing on the water-borne coating of the base material obtained by step (2), with obtain
Design for advertisement；
The preparation method of the water paint is：
By 6 grams of hydroxyethyl cellulose, 15 grams of acrylic emulsion, 0.5 gram of APES, 8 grams of second
Glycol, 3 grams of methyl-silicone oil, 7 grams of butyl, 5 grams of sulfonated polyether amine-sulfonated polyethersulfone block copolymer be with
And 100 grams deionized water add mixer in be sufficiently mixed after 20 minutes, discharging is obtained, wherein sulfonated polyether amine-sulphur
Change polyethersulfone block copolymer preparation method be：
(1) preparation of polyetheramine prepolymer
In the three-necked bottle that 1000mL is dried, 100 grams of octafluorobiphenyl diglycidyl ether (epoxide number is sequentially added
0.45mol/100g), 0.22mol benzylamine and 700 grams of dimethyl sulfoxide (DMSO)s, lead to nitrogen protection and magnetic agitation；1h is stirred at room temperature
Afterwards, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room temperature, obtains epoxy-capped polyetheramine pre-polymer solution；
(2) preparation of polyetheramine-sulfonated polyethersulfone block copolymer
In the three-necked bottle that 1000mL is dried, weigh respectively 0.0105mol sulfonation dichloro diphenyl sulfone, 0.01mol grams
4,4'- '-biphenyl diphenols, are dissolved in 50mL 1-METHYLPYRROLIDONE (NMP), add 0.03mol sodium carbonate and 20mL first
Benzene, lead to nitrogen protect 1 hour after, by reaction system at 180 DEG C sustained response 24 hours, be then down to room temperature, add
After 0.0005mol para-aminophenol, lead to nitrogen protect 1 hour after, by reaction system at 180 DEG C sustained response 12 hours
Afterwards, room temperature is down to, dark brown viscous liquid is obtained, the epoxy-capped polyetheramine prepolymer for then obtaining above-mentioned steps (1) is molten
Liquid all adds this reaction system, after leading to nitrogen protection 1 hour, heats up 80 DEG C after reacting 4 hours, reaction solution is poured into rapidly
In 2000mL deionized waters, a large amount of solid precipitations are obtained；With after the deionized water cyclic washing product, suction filtration simultaneously collects polymerization
Thing, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain polyetheramine-sulfonated polyethersulfone block copolymer；
(3) preparation of sulfonated polyether amine-sulfonated polyethersulfone block copolymer
Polyetheramine-sulfonated polyethersulfone block copolymer 1 gram obtained by taking step (2), is dissolved in the dense sulphur of mass fraction 98%
In acid, after being reacted 5 hours under ice bath, pour into frozen water, with after the frozen water cyclic washing product, suction filtration and collected polymer, in
In vacuum drying oven, 50 DEG C of dryings 24 hours obtain sulfonated polyether amine-sulfonated polyethersulfone block copolymer；
The preparation method of the water-base ink is：
By 3 grams of the black (MICROLITH of micro- high-tensile strength：Black) C-WA, 3 grams of pigment dispersing agent (sodium naphthalene sulfonate condensation product
(Ionet D-2) and dispersant A M-C weight ratio are 0.7: 1 mixture), 20 grams of glycerine, 3 grams of TW-20,0.02 gram
Fluoro-alkyl alkoxide compound (Fluorad Fc171), 5 grams of polyquaternium-polybenzimidazoles block copolymer and
100 grams of deionized water is added to be sufficiently mixed after 30 minutes in mixer, and discharging is obtained；
The preparation method of the polyquaternium-polybenzimidazoles block copolymer is：
(1) polyquaternium prepolymer is prepared
In the three-necked bottle that 1000ml is dried, 1,12- dibromo-dodecanes 0.1mol, Isosorbide-5-Nitrae-lupetazin are added
0.097mol and solvent dimethyl sulfoxide (DMSO) 80ml, at 50 DEG C after reaction 5 hours, vacuum distillation removes solvent and obtains polyquaternium
Prepolymer；
(2) polybenzimidazoles prepolymer is prepared
180g polyphosphoric acids is placed in 250ml three-neck flasks, connection nitrogen inlet, drying tube, nitrogen outlet and machinery
Agitator.After nitrogen is passed through 5 minutes, 0.01mol 3,3'- diaminobenzidines (DAB) are added in three-neck flask, treated
DAB is uniformly dispersed after being dissolved in polyphosphoric acids, adds 0.009mmol terephthalic acid (TPA)s, adds 20mmol's afterwards
P2O5 is used for the water generated in absorbing reaction, opens mechanical agitation and heats up simultaneously, keeps 200 DEG C of reaction 20h.Question response system temperature
Degree is cooled to after 150 DEG C, is poured into deionized water and is precipitated, and cyclic washing removes polyphosphoric acids.With a large amount of mass fractions 10%
Sodium hydrate aqueous solution agitator treating neutralizes the phosphoric acid of residual in 24 hours, then repeatedly removes hydroxide with deionization cyclic washing
Sodium.Gained is deposited in vacuum drying oven at 60 DEG C and dried, polybenzimidazoles prepolymer is produced；
(3) polyquaternium-polybenzimidazoles block copolymer is prepared
In the three-necked bottle that 1000ml is dried, polyquaternium prepolymer, 1 gram of step obtained by 1 gram of step (1) are sequentially added
(2) gained polybenzimidazoles prepolymer, 100ml dimethyl sulfoxide (DMSO)s and 2 grams of sodium carbonate, after being reacted 5 hours at 60 DEG C, are obtained
Clear yellow viscous solution, is down to after room temperature, pours into deionized water and precipitates, and with deionization cyclic washing repeatedly to neutral, then takes out
Filter, collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain polyquaternium-polybenzimidazoles block copolymer.
Embodiment 10
Water paint coating liquid is sprayed on to the surface of advertising cloth with the method for spraying, with roll shaft by advertising cloth face coat
Roll it is even roll reality, dried in baking oven, drying temperature be 80 degrees Celsius, drying time be 50 minutes；
With ink jet printer by water-base ink inkjet printing on the water-borne coating of the base material obtained by step (2), with obtain
Design for advertisement；
The preparation method of the water paint is：
By 6 grams of hydroxyethyl cellulose, 15 grams of acrylic emulsion, 0.5 gram of APES, 8 grams of second
Glycol, 3 grams of methyl-silicone oil, 7 grams of butyl, 5 grams of sulfonated polyether amine-sulfonated polyethersulfone block copolymer be with
And 100 grams deionized water add mixer in be sufficiently mixed after 20 minutes, discharging is obtained, wherein sulfonated polyether amine-sulphur
Change polyethersulfone block copolymer preparation method be：
(1) preparation of polyetheramine prepolymer
In the three-necked bottle that 1000mL is dried, 100 grams of octafluorobiphenyl diglycidyl ether (epoxide number is sequentially added
0.45mol/100g), 0.22mol benzylamine and 700 grams of dimethyl sulfoxide (DMSO)s, lead to nitrogen protection and magnetic agitation；1h is stirred at room temperature
Afterwards, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room temperature, obtains epoxy-capped polyetheramine pre-polymer solution；
(2) preparation of polyetheramine-sulfonated polyethersulfone block copolymer
In the three-necked bottle that 1000mL is dried, weigh respectively 0.0105mol sulfonation dichloro diphenyl sulfone, 0.01mol grams
4,4'- '-biphenyl diphenols, are dissolved in 50mL 1-METHYLPYRROLIDONE (NMP), add 0.03mol sodium carbonate and 20mL first
Benzene, lead to nitrogen protect 1 hour after, by reaction system at 180 DEG C sustained response 24 hours, be then down to room temperature, add
After 0.0005mol para-aminophenol, lead to nitrogen protect 1 hour after, by reaction system at 180 DEG C sustained response 12 hours
Afterwards, room temperature is down to, dark brown viscous liquid is obtained, the epoxy-capped polyetheramine prepolymer for then obtaining above-mentioned steps (1) is molten
Liquid all adds this reaction system, after leading to nitrogen protection 1 hour, heats up 80 DEG C after reacting 4 hours, reaction solution is poured into rapidly
In 2000mL deionized waters, a large amount of solid precipitations are obtained；With after the deionized water cyclic washing product, suction filtration simultaneously collects polymerization
Thing, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain polyetheramine-sulfonated polyethersulfone block copolymer；
(3) preparation of sulfonated polyether amine-sulfonated polyethersulfone block copolymer
Polyetheramine-sulfonated polyethersulfone block copolymer 1 gram obtained by taking step (2), is dissolved in the dense sulphur of mass fraction 98%
In acid, after being reacted 5 hours under ice bath, pour into frozen water, with after the frozen water cyclic washing product, suction filtration and collected polymer, in
In vacuum drying oven, 50 DEG C of dryings 24 hours obtain sulfonated polyether amine-sulfonated polyethersulfone block copolymer；
The preparation method of the water-base ink is：
By 3 grams of the black (MICROLITH of micro- high-tensile strength：Black) C-WA, 3 grams of pigment dispersing agent (sodium naphthalene sulfonate condensation product
(Ionet D-2) and dispersant A M-C weight ratio are 0.7: 1 mixture), 20 grams of glycerine, 3 grams of TW-20,0.02 gram
Fluoro-alkyl alkoxide compound (Fluorad Fc171), 3 grams of polyquaternium-polybenzimidazoles block copolymer and
100 grams of deionized water is added to be sufficiently mixed after 30 minutes in mixer, and discharging is obtained；
The preparation method of the polyquaternium-polybenzimidazoles block copolymer is：
(1) polyquaternium prepolymer is prepared
In the three-necked bottle that 1000ml is dried, 1,12- dibromo-dodecanes 0.1mol, Isosorbide-5-Nitrae-lupetazin are added
0.097mol and solvent dimethyl sulfoxide (DMSO) 80ml, at 50 DEG C after reaction 5 hours, vacuum distillation removes solvent and obtains polyquaternium
Prepolymer；
(2) polybenzimidazoles prepolymer is prepared
180g polyphosphoric acids is placed in 250ml three-neck flasks, connection nitrogen inlet, drying tube, nitrogen outlet and machinery
Agitator.After nitrogen is passed through 5 minutes, 0.01mol 3,3'- diaminobenzidines (DAB) are added in three-neck flask, treated
DAB is uniformly dispersed after being dissolved in polyphosphoric acids, adds 0.009mmol terephthalic acid (TPA)s, adds 20mmol's afterwards
P2O5 is used for the water generated in absorbing reaction, opens mechanical agitation and heats up simultaneously, keeps 200 DEG C of reaction 20h.Question response system temperature
Degree is cooled to after 150 DEG C, is poured into deionized water and is precipitated, and cyclic washing removes polyphosphoric acids.With a large amount of mass fractions 10%
Sodium hydrate aqueous solution agitator treating neutralizes the phosphoric acid of residual in 24 hours, then repeatedly removes hydroxide with deionization cyclic washing
Sodium.Gained is deposited in vacuum drying oven at 60 DEG C and dried, polybenzimidazoles prepolymer is produced；
(3) polyquaternium-polybenzimidazoles block copolymer is prepared
In the three-necked bottle that 1000ml is dried, polyquaternium prepolymer, 1 gram of step obtained by 1 gram of step (1) are sequentially added
(2) gained polybenzimidazoles prepolymer, 100ml dimethyl sulfoxide (DMSO)s and 2 grams of sodium carbonate, after being reacted 5 hours at 60 DEG C, are obtained
Clear yellow viscous solution, is down to after room temperature, pours into deionized water and precipitates, and with deionization cyclic washing repeatedly to neutral, then takes out
Filter, collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain polyquaternium-polybenzimidazoles block copolymer.
Embodiment 11
Water paint coating liquid is sprayed on to the surface of advertising cloth with the method for spraying, with roll shaft by advertising cloth face coat
Roll it is even roll reality, dried in baking oven, drying temperature be 80 degrees Celsius, drying time be 50 minutes；
With ink jet printer by water-base ink inkjet printing on the water-borne coating of the base material obtained by step (2), with obtain
Design for advertisement；
The preparation method of the water paint is：
By 6 grams of hydroxyethyl cellulose, 15 grams of acrylic emulsion, 0.5 gram of APES, 8 grams of second
Glycol, 3 grams of methyl-silicone oil, 7 grams of butyl, 5 grams of sulfonated polyether amine-sulfonated polyethersulfone block copolymer be with
And 100 grams deionized water add mixer in be sufficiently mixed after 20 minutes, discharging is obtained, wherein sulfonated polyether amine-sulphur
Change polyethersulfone block copolymer preparation method be：
(1) preparation of polyetheramine prepolymer
In the three-necked bottle that 1000mL is dried, 100 grams of octafluorobiphenyl diglycidyl ether (epoxide number is sequentially added
0.45mol/100g), 0.22mol benzylamine and 700 grams of dimethyl sulfoxide (DMSO)s, lead to nitrogen protection and magnetic agitation；1h is stirred at room temperature
Afterwards, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room temperature, obtains epoxy-capped polyetheramine pre-polymer solution；
(2) preparation of polyetheramine-sulfonated polyethersulfone block copolymer
In the three-necked bottle that 1000mL is dried, weigh respectively 0.0105mol sulfonation dichloro diphenyl sulfone, 0.01mol grams
4,4'- '-biphenyl diphenols, are dissolved in 50mL 1-METHYLPYRROLIDONE (NMP), add 0.03mol sodium carbonate and 20mL first
Benzene, lead to nitrogen protect 1 hour after, by reaction system at 180 DEG C sustained response 24 hours, be then down to room temperature, add
After 0.0005mol para-aminophenol, lead to nitrogen protect 1 hour after, by reaction system at 180 DEG C sustained response 12 hours
Afterwards, room temperature is down to, dark brown viscous liquid is obtained, the epoxy-capped polyetheramine prepolymer for then obtaining above-mentioned steps (1) is molten
Liquid all adds this reaction system, after leading to nitrogen protection 1 hour, heats up 80 DEG C after reacting 4 hours, reaction solution is poured into rapidly
In 2000mL deionized waters, a large amount of solid precipitations are obtained；With after the deionized water cyclic washing product, suction filtration simultaneously collects polymerization
Thing, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain polyetheramine-sulfonated polyethersulfone block copolymer；
(3) preparation of sulfonated polyether amine-sulfonated polyethersulfone block copolymer
Polyetheramine-sulfonated polyethersulfone block copolymer 1 gram obtained by taking step (2), is dissolved in the dense sulphur of mass fraction 98%
In acid, after being reacted 5 hours under ice bath, pour into frozen water, with after the frozen water cyclic washing product, suction filtration and collected polymer, in
In vacuum drying oven, 50 DEG C of dryings 24 hours obtain sulfonated polyether amine-sulfonated polyethersulfone block copolymer；
The preparation method of the water-base ink is：
By 3 grams of the black (MICROLITH of micro- high-tensile strength：Black) C-WA, 3 grams of pigment dispersing agent (sodium naphthalene sulfonate condensation product
(Ionet D-2) and dispersant A M-C weight ratio are 0.7: 1 mixture), 20 grams of glycerine, 3 grams of TW-20,0.02 gram
Fluoro-alkyl alkoxide compound (Fluorad Fc171), 3 grams of polyquaternium-polybenzimidazoles block copolymer, 5 grams
Sulfonated polyether ketone modified graphene oxide and 100 grams deionized water add mixer in be sufficiently mixed after 30 minutes, go out
Material is obtained；
The preparation method of the polyquaternium-polybenzimidazoles block copolymer is：
(1) polyquaternium prepolymer is prepared
In the three-necked bottle that 1000ml is dried, 1,12- dibromo-dodecanes 0.1mol, Isosorbide-5-Nitrae-lupetazin are added
0.097mol and solvent dimethyl sulfoxide (DMSO) 80ml, at 50 DEG C after reaction 5 hours, vacuum distillation removes solvent and obtains polyquaternium
Prepolymer；
(2) polybenzimidazoles prepolymer is prepared
180g polyphosphoric acids is placed in 250ml three-neck flasks, connection nitrogen inlet, drying tube, nitrogen outlet and machinery
Agitator.After nitrogen is passed through 5 minutes, 0.01mol 3,3'- diaminobenzidines (DAB) are added in three-neck flask, treated
DAB is uniformly dispersed after being dissolved in polyphosphoric acids, adds 0.009mmol terephthalic acid (TPA)s, adds 20mmol's afterwards
P2O5 is used for the water generated in absorbing reaction, opens mechanical agitation and heats up simultaneously, keeps 200 DEG C of reaction 20h.Question response system temperature
Degree is cooled to after 150 DEG C, is poured into deionized water and is precipitated, and cyclic washing removes polyphosphoric acids.With a large amount of mass fractions 10%
Sodium hydrate aqueous solution agitator treating neutralizes the phosphoric acid of residual in 24 hours, then repeatedly removes hydroxide with deionization cyclic washing
Sodium.Gained is deposited in vacuum drying oven at 60 DEG C and dried, polybenzimidazoles prepolymer is produced；
(3) polyquaternium-polybenzimidazoles block copolymer is prepared
In the three-necked bottle that 1000ml is dried, polyquaternium prepolymer, 1 gram of step obtained by 1 gram of step (1) are sequentially added
(2) gained polybenzimidazoles prepolymer, 100ml dimethyl sulfoxide (DMSO)s and 2 grams of sodium carbonate, after being reacted 5 hours at 60 DEG C, are obtained
Clear yellow viscous solution, is down to after room temperature, pours into deionized water and precipitates, and with deionization cyclic washing repeatedly to neutral, then takes out
Filter, collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain polyquaternium-polybenzimidazoles block copolymer；
The preparation method of the sulfonated polyether ketone modified graphene oxide is：
In the three-necked bottle that 1000mL is dried, 0.0106mol sulfonation 4 is weighed respectively, 4'- difluoro benzophenones,
0.01mol grams of 4,4'- '-biphenyl diphenols, are dissolved in 50mL 1-METHYLPYRROLIDONE (NMP), add 0.03mol carbonic acid
The toluene of sodium and 20mL, lead to nitrogen protect 1 hour after, by reaction system at 180 DEG C sustained response 24 hours, be then down to room
Temperature, add 0.0006mol para-aminophenol after, lead to nitrogen protect 1 hour after, by reaction system at 180 DEG C sustained response
After 12 hours, be down to room temperature, obtain dark brown viscous liquid, then into this reaction system add 30 grams of graphene oxides and
5 grams of KH-560, lead to nitrogen protect 1 hour after, heat up 80 DEG C reaction 4 hours after, reaction solution is poured into rapidly 2000mL go from
In sub- water, a large amount of solid precipitations are obtained；With after the deionized water cyclic washing product, suction filtration and collected polymer dry in vacuum
In case, 50 DEG C of dryings 24 hours obtain sulfonated polyether ketone modified graphene oxide.
Method of testing
Weatherability is tested：
Cause weatherability reduction to be mainly the ozone in daylight middle-ultraviolet lamp and air, easy Exposure to Sunlight jail is proposed accordingly
Spend method of testing and ozone proof method of testing.Through repetition test gradual perfection test process.Using the principle of aberration to the party
Method has added quantitative assessment, and contact between aberration and light fastness rank and resistance to ozone level is set up by analysis, can be with
The rank of light fastness, resistance to ozone level, simple and fast are extrapolated by attenuation rate or value of chromatism Δ E.Use optics scenograph
Eye-one test cases 1, example 2, example 3, example 4, example 5 print the color density of color lump, then under uv lamps according to 3 hours,
Its color density is being tested, color density attenuation rate of the color lump after UV lamp pre-irradiation is calculated.Color density attenuation rate is bigger, shows sun-proof
Property is poorer.On the contrary, color density attenuation rate is lower, light resistance is better.
The color density of color lump is printed with optics scenograph Eye-one test cases 1, example 2, example 3, example 4, example 5,
Then (ozone disinfection cabinet) 3 hours under ozone environment, are testing its color density, calculate color lump before and after ozone disinfection cabinet storage
Color density attenuation rate.Color density attenuation rate is bigger, shows that resistance to ozone is poorer.On the contrary, color density attenuation rate is lower, resistance to ozone is got over
It is good.
Attenuation rate=(color density after original color density-test)/original color density
Water resistance is detected：
Detection method：One section of the advertising cloth of inkjet printing is intercepted, is impregnated in 50 DEG C of deionized water, observation ink fades
And diffusion time, and record.Impregnate 24h after, take out spontaneously dry, and with untreated samples ready visual contrast.
Salt tolerant acidity detection：
Detection method：One section of the advertising cloth of inkjet printing is intercepted, 24h is impregnated in 10% (volume ratio) aqueous hydrochloric acid solution
Afterwards, impregnate 10min in deionized water, take out and spontaneously dry, and with untreated samples ready visual contrast.
Resistance to alcohol repellency detection：
Detection method：One section of the advertising cloth of inkjet printing is intercepted, 20min is impregnated in 50% (volume ratio) ethanol water
Afterwards, take out spontaneously dry, and with untreated samples ready visual contrast.
The aqueous detection of resistant to ammonia：
Detection method：One section of the advertising cloth of inkjet printing is intercepted, 24h is impregnated in 10% (mass percent) ammonia spirit
Afterwards, impregnate 20min in deionized water, take out and spontaneously dry, and with untreated samples ready visual contrast.
The heat-resisting quantity detection of ink:
Detection method：One section of the advertising cloth of inkjet printing is intercepted, is placed in the 100 DEG C of boiling water boiled, dipping is boiled after 10min
Take out, spontaneously dry, and with untreated samples ready visual contrast.
Ink lower temperature resistance is detected：
Detection method：Tested ink is poured into cold-resistant Packaging Bottle, is put into (- 20 ± 1) DEG C cryostat to 24h and is taken
Go out, return to after room temperature, detect its print performance.
The wearability detection of ink：
Detection method：Rubbed same number with coin on pattern, and until there is a kind of writing abrasion mark occur, record rubs
Wipe number of times.With the strength typically scratched, the angle on 45 degree of coin and word surface is set to be scratched back and forth on the surface of word, until there is one kind
Writing surface occurs scratching vestige, and record scratches number of times, determines wearability.
Test result is shown in Table 1.
Table 1
Data above can be seen that compared with conventional method, and the ink-jet pattern obtained using the inventive method has obvious
Better performance, thus provides the advantageous effects of the present invention.
Claims (10)
1. water-base ink indoors and outdoor inkjet printing design for advertisement method, it is characterised in that comprise the following steps：
(1) base material is provided, the base material is advertising cloth and/or poster paper；
(2) water paint is coated at least one surface of the base material；
(3) by water-base ink inkjet printing on the water-borne coating of the base material obtained by step (2), to obtain design for advertisement.
2. according to the method described in claim 1, it is characterised in that the water paint, in parts by weight, its preparing raw material bag
Containing following components：
3. method according to claim 2, it is characterised in that the water paint, in parts by weight, its preparing raw material is also
Comprising：3-8 parts of sulfonated polyether amine-sulfonated polyethersulfone block copolymer.
4. according to the method described in claim 1, it is characterised in that the water-base ink, in parts by weight, its preparing raw material bag
Containing following components：
5. method according to claim 4, it is characterised in that the water-base ink, in parts by weight, its preparing raw material is also
Comprising：1-5 parts of polyquaternium-polybenzimidazoles block copolymer.
6. method according to claim 4, it is characterised in that the pigment is selected from the black (MICROLITH of micro- high-tensile strength：
Black) C-WA, the black (MICROLITH of micro- high-tensile strength：Black) C-K, carbon black, the red (MICROLITH of micro- high-tensile strength：Red) B-WA, micro- high
Red (the MICROLITH of power：Red) 4C-K, micro- high-tensile strength indigo plant (MICROLITH：Blue) 4G-WA, micro- high-tensile strength indigo plant (MICROLITH：
Blue) A3R-K, micro- high-tensile strength Huang (MICROLITH：Yellow) BAW-WA and micro- high-tensile strength Huang (MICROLITH：Yellow)3R-K
At least one of.
7. method according to claim 4, it is characterised in that the pigment dispersing agent is sodium naphthalene sulfonate condensation product (Ionet
D-2) the mixture for being 0.6-0.9: 1 with dispersant A M-C weight ratio.
8. method according to claim 4, it is characterised in that other auxiliary agents are TW-20 and/or QPE-20.
9. method according to claim 4, it is characterised in that the NMF is selected from glycerine, ethylene glycol, propane diols, poly-
At least one of ethylene glycol, diethylene glycol (DEG), triethylene glycol and sorbierite.
10. method according to claim 4, it is characterised in that the surfactant is fluoro-alkyl alkoxy chemical combination
Thing (Fluorad Fc171) or fluoroalkyl (Fluorad Fc430).
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